Sources, Fate and Transformation of Organic Matter in Wetlands and Estuaries

Dissolved organic matter (DOM) is a complex mixture of organic compounds and represents the largest reservoirs of carbon (C) on earth. Particulate organic matter (POM) is another important carbon component in C cycling and controls a variety of biogeochemical processes. Estuaries, as important interfaces between land and ocean, play important roles in retaining and transforming such organic matter (OM) and serve as both sources and sinks of DOM and POM. There is a diverse array of both autochthonous and allochthonous OM sources in wetland/estuarine ecosystems. A comprehensive study on the sources, transformation and fate of OM in such ecosystems is essential in advancing our understanding of C cycling and better constraining the global C budget. In this work, DOM characteristics were investigated in different estuaries. Dissolved organic matter source strengths and dynamics were assessed in a seagrass-dominated subtropical estuarine lagoon. DOM dynamics controlled by hydrology and seagrass primary productivity were confirmed, and the primary source of DOM was quantified using the combination of excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC) and stable C isotope analysis. Seagrass can contribute up to 72% of the DOM in the study area. The spatial and temporal variation of DOM dynamics was also studied in a freshwated dominated estuary fringed with extensive salt marshes. The data showed that DOM was primarily derived from freshwater marshes and controlled by hydrology while salt marsh plants play a significant role in structuring the distribution patterns of DOM quality and quantity. The OM dynamics was also investigated in a mangrove-dominate estuary and a comparative study was conducted between the DOM and POM pools. The results revealed both similarity and dissimilarity in DOM and POM composition. The dynamics of both OM pools are largely uncoupled as a result of source differences. Fringe mangrove swamps are suggested to export similar amounts of DOM and POM and should be considered as an important source in coastal C budgets. Lastly, chemical characterizations were conducted on the featured fluorescence component in OM in an attempt to better understand the composition and origins of the specific PARAFAC component. The traditionally defined ‘protein-like’ fluorescence was found to contain both proteinaceous and phenolic compounds, suggesting that the application of this parameter as a proxy for amino acid content and bioavailability may be limited.

The development of calibrants through characterization of volatile organic compounds from peroxide based explosives and a non-target chemical calibration compound

Detection canines represent the fastest and most versatile means of illicit material detection. This research endeavor in its most simplistic form is the improvement of detection canines through training, training aids, and calibration. This study focuses on developing a universal calibration compound for which all detection canines, regardless of detection substance, can be tested daily to ensure that they are working with acceptable parameters. Surrogate continuation aids (SCAs) were developed for peroxide based explosives along with the validation of the SCAs already developed within the International Forensic Research Institute (IFRI) prototype surrogate explosives kit. Storage parameters of the SCAs were evaluated to give recommendations to the detection canine community on the best possible training aid storage solution that minimizes the likelihood of contamination. Two commonly used and accepted detection canine imprinting methods were also evaluated for the speed in which the canine is trained and their reliability. As a result of the completion of this study, SCAs have been developed for explosive detection canine use covering: peroxide based explosives, TNT based explosives, nitroglycerin based explosives, tagged explosives, plasticized explosives, and smokeless powders. Through the use of these surrogate continuation aids a more uniform and reliable system of training can be implemented in the field than is currently used today. By examining the storage parameters of the SCAs, an ideal storage system has been developed using three levels of containment for the reduction of possible contamination. The developed calibration compound will ease the growing concerns over the legality and reliability of detection canine use by detailing the daily working parameters of the canine, allowing for Daubert rules of evidence admissibility to be applied. Through canine field testing, it has been shown that the IFRI SCAs outperform other commercially available training aids on the market. Additionally, of the imprinting methods tested, no difference was found in the speed in which the canines are trained or their reliability to detect illicit materials. Therefore, if the recommendations discovered in this study are followed, the detection canine community will greatly benefit through the use of scientifically validated training techniques and training aids.

The Development of Calibrants through Characterization of Volatile Organic Compounds from Peroxide Based Explosives and a Non-target Chemical Calibration Compound

Detection canines represent the fastest and most versatile means of illicit material detection. This research endeavor in its most simplistic form is the improvement of detection canines through training, training aids, and calibration. This study focuses on developing a universal calibration compound for which all detection canines, regardless of detection substance, can be tested daily to ensure that they are working with acceptable parameters. Surrogate continuation aids (SCAs) were developed for peroxide based explosives along with the validation of the SCAs already developed within the International Forensic Research Institute (IFRI) prototype surrogate explosives kit. Storage parameters of the SCAs were evaluated to give recommendations to the detection canine community on the best possible training aid storage solution that minimizes the likelihood of contamination. Two commonly used and accepted detection canine imprinting methods were also evaluated for the speed in which the canine is trained and their reliability. As a result of the completion of this study, SCAs have been developed for explosive detection canine use covering: peroxide based explosives, TNT based explosives, nitroglycerin based explosives, tagged explosives, plasticized explosives, and smokeless powders. Through the use of these surrogate continuation aids a more uniform and reliable system of training can be implemented in the field than is currently used today. By examining the storage parameters of the SCAs, an ideal storage system has been developed using three levels of containment for the reduction of possible contamination. The developed calibration compound will ease the growing concerns over the legality and reliability of detection canine use by detailing the daily working parameters of the canine, allowing for Daubert rules of evidence admissibility to be applied. Through canine field testing, it has been shown that the IFRI SCAs outperform other commercially available training aids on the market. Additionally, of the imprinting methods tested, no difference was found in the speed in which the canines are trained or their reliability to detect illicit materials. Therefore, if the recommendations discovered in this study are followed, the detection canine community will greatly benefit through the use of scientifically validated training techniques and training aids.

Identification of characteristic volatile organic compounds released during the decomposition process of human remains and analogues

The manner in which remains decompose has been and is currently being researched around the world, yet little is still known about the generated scent of death. In fact, it was not until the Casey Anthony trial that research on the odor released from decomposing remains, and the compounds that it is comprised of, was brought to light. The Anthony trial marked the first admission of human decomposition odor as forensic evidence into the court of law; however, it was not "ready for prime time" as the scientific research on the scent of death is still in its infancy. This research employed the use of solid-phase microextraction (SPME) with gas chromatography-mass spectrometry (GC-MS) to identify the volatile organic compounds (VOCs) released from decomposing remains and to assess the impact that different environmental conditions had on the scent of death. Using human cadaver analogues, it was discovered that the environment in which the remains were exposed to dramatically affected the odors released by either modifying the compounds that it was comprised of or by enhancing/hindering the amount that was liberated. In addition, the VOCs released during the different stages of the decomposition process for both human remains and analogues were evaluated. Statistical analysis showed correlations between the stage of decay and the VOCs generated, such that each phase of decomposition was distinguishable based upon the type and abundance of compounds that comprised the odor. This study has provided new insight into the scent of death and the factors that can dramatically affect it, specifically, frozen, aquatic, and soil environments. Moreover, the results revealed that different stages of decomposition were distinguishable based upon the type and total mass of each compound present. Thus, based upon these findings, it is suggested that the training aids that are employed for human remains detection (HRD) canines should 1) be characteristic of remains that have undergone decomposition in different environmental settings, and 2) represent each stage of decay, to ensure that the HRD canines have been trained to the various odors that they are likely to encounter in an operational situation.

Characterization, sources, and transformations of dissolved organic matter (DOM) in Florida coastal Everglades (FCE)

Dissolved organic matter (DOM) is one of the largest carbon reservoirs on this planet and is present in aquatic environments as a highly complex mixture of organic compounds. The Florida coastal Everglades (FCE) is one of the largest wetlands in the world. DOM in this system is an important biogeochemical component as most of the nitrogen (N) and phosphorous (P) are in organic forms. Achieving a better understanding of DOM dynamics in large coastal wetlands is critical, and a particularly important issue in the context of Everglades restoration. In this work, the environmental dynamics of surface water DOM on spatial and temporal scales was investigated. In addition, photo- and bio-reactivity of this DOM was determined, surface-to-groundwater exchange of DOM was investigated, and the size distribution of freshwater DOM in Everglades was assessed. The data show that DOM dynamics in this ecosystem are controlled by both hydrological and ecological drivers and are clearly different on spatial scales and variable seasonally. The DOM reactivity data, modeled with a multi-pool first order degradation kinetics model, found that fluorescent DOM in FCE is generally photo-reactive and bio-refractory. Yet the sequential degradation proved a “priming effect” of sunlight on the bacterial uptake and reworking of this subtropical wetland DOM. Interestingly, specific PARAFAC components were found to have different photo- and bio-degradation rates, suggesting a highly heterogeneous nature of fluorophores associated with the DOM. Surface-to-groundwater exchange of DOM was observed in different regions of the system, and compositional differences were associated with source and photo-reactivity. Lastly, the high degree of heterogeneity of DOM associated fluorophores suggested based on the degradation studies was confirmed through the EEM-PARAFAC analysis of DOM along a molecular size continuum, suggesting that the fluorescence characteristics of DOM are highly controlled by different size fractions and as such can exhibit significant differences in reactivity.